Celluloid compound.



UNITED STATES Patented April 26, 1904;

PATENT OFFICE.

ALBRECHT SCHMIDT, OF HOCHST-ON-THE-MAIN, GERMANY, ASSIGNOR TO THE FARBW'ERKE, VORM. MEISTER, LUCIUS & BRIZTNING, OF HOOHST-' ON-THE-MAIN, GERMANY, A CORPORATION OF GERMANY.

OELLULOID COMPOUND.

SPECIFICATION forming part of Letters Patent No. 758,335, dated April 26, 1904. Application filed January 12, 1900. Serial No. 1,185. (No specimens.)

To aZZ whom it may concern.-

Be it known that I, ALBRECHT Scrrnnnr, Ph. 1)., a citizen of the Empire of Germany, residing at Hochst-on-the-Main, Germany, have 5 invented certain new anduseful Improvements in Celluloid Compounds, of which the following is a specification.

In the manufacture of celluloid experiments looking to the substitution of the camphor I heretofore employed by a cheap and 'inodorous equivalent have hitherto met with little practical result, for the properties required in a carnphor substitute are numerous, and camphor alone has hitherto been found to include all these necessary properties. Such substances, however, which may be employed in. the art referred to as a camphor substitute I have found in the derivatives of aromatic sulfonic acids of the general formula R SOaA. In this formula, R represents an aromatic radical or its substitution product-such, for instance as phenyl, tolyl, xylyl, naphthyl, nitrophenyl, nitrotolyl, alliyloxyphenyl, &c. and A indicates either an aliphatic or aromatic- 5 ether residue, such as oxyalkyl or residue of mono or poly valent alcohoifor instance, OHBOH, C2H5OH, CtHsCI'IzOH, OII-z(OH)- CH(OH)-OH2(OH,) &c.and oxyal:phyl or residue of a mono or poly valent phenoL'such 3 as phenol, naphthoi, cresol, resorcinol, dioxydiphenylmethane, &c., or a NH2 group, which, non-substituted, may be substituted once or H2C6H5, 86C. Bodies of this kindare, for instance:

R so A Para (JH .C3,,H SO OU H p.tolu01su1fonic acid ethylester Para CH O H, -SO OC,,H,, p-toluolsulfonic acid phenylester Para CH B I'L, SO N'HO.;H pt0luolsulfomonoethylamid Para. OH CJL S0 NHC,,H p-toluoisulfomonophenylamid Para OH;,.C,;H -SO N C H r, p-toluolsulfodiethylamid.

Thus, for instance, the derivatives obtained 5 from the para-toluenesulfonic-chlorid (the byproduct in the manufacture of saccharine) such was alkyl-paratoluenesulfonate, ethyl- I k para-toluenesulfonate, glyceryl-para-toluene sulfonate, &c., alphyl-paratoluenesulfonate, 5 5 (phenylpara toluenesulfonate, cresyl paratoluenesulfonate, &c.,) para-toluenesulfona mids, such as para-toluenesulfanilid, para-toluenesulfethylanilid, and para-toluenesulfonic alkyl and dialkyl-an1ids-are capable alone or 0 in mixtures of serving as a substitute for cam, phor. 7 Also the derivatives obtained from disulfonic-acid chlorids are valuable. In some cases it is advisable to mix two or more of the abovenamed substances or in mixture 5 with camphor, especially with such RSOz-A bodies as by themselves dissolve too li'ttle'nitrocellulose and possess too great a power of crystallizationfor instance, with non-substituted alphyl-sulfamids, which, when em- 7 ployed by themselves cannot without'difiiculty be Worked with nitrocellulose. By this mix ture' of a certain percentage the power of dissolving nitrocellulose is increased and the tendency to crystallize is reduced. The process is exactly the same as in the manufacture of celluloid, except for this difference only that the sulfo derivatives in question are wholly. or partly substituted for camphor. In all these substances the group B-SO2+ is characteristic for its dissolving Thus, for. instance, instead of thirty about thirty to forty per cent. of the sulfo derivative in question is employed, or, for in- I stance,twenty per cent. of camphor and twenty per cent. of the sulfo derivative. Experiments were made with a great number of different substances, from which a law was deduced showing that all substances of the same class 9 are suitable as a substitute for camphor. All

of these substances belong to one and the same parent substance, the body having the power to dissolve nitrocellulose being thoughout the SO2. This group is combined with group R the group A-for instance, an oxalkyl, (for instance, CtHfiSOzOOHgl in some with an 0xalphyl, (for instance, CGHE SO2OCGHE,) and in some with NH2, (for instance, G6H.)' SO2NH2,) or with NHCGHB, (for instance, CuHaSOz-NHCeHa).

The following are mentioned as some of the substances operated with:

Melting-point in degrees centigrade.

Benzenesulfamid 153 Para-chlorbenzenesulfamid 144-145 Para-toluenesulfamid 137 Benzenesulfethylamid 58- 59 Benzenesulfdiethylamid 43 Para-toluenesulfo-ethylamid. 58

Para-toluenesulfo-diethylamid Acet-benzenesulfoamid. 126-127 Acet-para-toluenesulfamid 8-139 Benzoyl-benzenesulfamid 147-148 Benzoyl-para-toluenesulfamid 147 148 Dibenzyl-benzenesulfamid p Dibenzyl-para-toluenesulfamid 115-116 Dibenzy1para-toluenesulfoimid 171-172 Dibenzenesu1foimid 157-158 Benzenesulfanilid 110 Y Para-chlorbenzenesulfani 105-106 Dibenzyl-para-chlorbenzenes fa 143-144 Para-toluenesulfanilid 103 Dibenzyl-para-toluenesulfanilid. 180-181 Benzenesulfo-methylanilid 79 Benzenesulfo-etnylanilid i1 Benzenesulfo-orlho-toluid. 125-126 Benzenesulfo-para-toluid 121-122 Benzenesulfo-para-ch10rani1id 121-122 Benzenesulfo-orthohenetidin 104-105 Benzenesulfo-para-p enetidin... 141-142 Benzenesulfo-alpha-nafihth lamid 167-168 Benzenesulfo-beta-nap thy amin 99-100 Benzencsulfo-di henylamin 126-127 Para-toluenesulto-methylanilid. 95

Para-toluenesulfo-ethylanilid 87- Para-toluenesulfo-ortho-toluid 109-110 Para-toluenesulfo-para-toluid 118-119 Para-tolnenesulfo-meta-xylidid 105-106 Para-toluenesulfo-para-chloranih 95- 96 Para-toluenesulfo-orthohenetidiiL 153-154 Para-toluenesulfo-para-p enetidin 107-108 Para-toluenesulfo-alpha-naghth lamin 157-158 Para-toluenesulfo-beta-nap thy amin 133-134 Para-toluenesulfo-diphen lamin 14 -144 Para-toluenesulfo-phenyl ydrazi 1 5-156 Benzenesulfo-acidphenylether 34- 35 Para-toluenesulfo-acidphenyleth 95- 96 Benzenesulfo-para-cresol. 44- 45 Para-toluenesulfo-cresol 69- 70 Benzenesulfo-beta-na htho1 106-107 Para-toluenesulfonap tho] 124-125 Para-toluenesulfo-alpha-naphthol 91 Para-chlorbenzenesu fo-beta-naphtliol 128 429 Dibenzenesulfo-2.7-dioxynaphthalin 122-123 Di-para-to]uenesulf0-2.7-dioxynaphthalin 150-151 Para-chlorbenzenesulfo-anilid 104 Parat0luenesulfamido acetic acid 147-148 Para-toluenesulfamidoethylester 6(3- 67 Para-toIuenesulfoacidethylester 32- 3d Ortho-sulfamidobenzoic acid 154-155 Meta-sulfamidobenzoic acid 246-247 Para-sulfamidobenzoic acid 280 Ortho-sulfamidoethylester 82- 83 Para-sulfamidoamylester 116-117 Meta-sulfamidoethylester 125-126 Para-sulfamidoethylester 110-111 The manufacture of the new celluloid-like compounds is effected in the same manner as is usual with camphor celluloid in other countriesfor instance,by applying heat, pressure, and dissolving nitrated cellulose (pyroxylin, &c.) in one of the above-mentioned moltencamphor substitutes or by a thorough mixture with same, with or without addition of a liquid solvent hitherto used in the manufacture of celluloid-such as ethylalcohol, woodspirit, acetone, &c.also, for instance, by dissolving the nitrated cellulose or by allowing it to swell up in a solution of one of the above-stated camphor substitutes in ethylalcohol, wood-spirit, acetone, &c., in fact, in

of the above-cited class of bodies, as well as I a mixture of these bodies with camphor, may be employed. Thus, for instance, a mixture of para-toluenesulfamid and para-toluenesulfomonoethylamid. I

To illustrate the above methods of making the new celluloid-like compounds, the following example is given:

Example: Pyroxylin (for instance, nitrated paper) in a condition suitable for the manufacture of celluloid is mixed with paratoluenesulfomonoethylamid,(paraCH3.C6H4 SO2NHC2H5,) for instance, in the proportion of about sixty to forty or is allowed to swell up with an addition of ethylalcohol, woodspirit, or acetone, &c. The mass thus treated with para-toluenesulfomonoethylamid is then further worked up in the usual manner of manufacturing celluloidfor instance, rolled out by means of a suitable roller to the thickness desired and pressed, or instead of being rolled out the mass while warm may be subjected to pressure in suitable molds and thereby forms of a desired shape obtained.

The example is the same if camphor is substituted for half of the para -toluenesulfomonoethylamid.

Any suitable known organic or inorganic admixtures may be added during the process of manufacture described for coloring or otherwise, according to the purpose they are I Having thus described my invention, I claim.

as new and desire to secure by Letters Patent As a new product, a celluloid-like compound composed of a mixture of nitrocellulose and /SO2A, a substance containing the group R SO2 wherein R means an alphyl-sulfonic group linked to A, an organic radical, substantially as described.

In testimony that I claim the foregoing as my inventionI have signed my name in presence of two subscribing witnesses.

, ALBRECHT SCHMIDT.

Witnesses:

HEINRICH HAHN, ALFRED BRISBOIS. 

